Systems and methods for screening solvents for dissolving tank bottom sludge

ABSTRACT

A method of screening solvents for the solubilization of petroleum hydrocarbons is disclosed. The method includes dissolving petroleum hydrocarbons in a selected solvent to form a first solution, adding an ionic liquid to the first solution and blending to form a second solution and measuring absorbance of the second solution using spectroscopic techniques. The solubilization of petroleum hydrocarbons in the solvent is then determined based on the difference between the measured absorbance of the first and second solution. A system for screening solvents for the solubilization of petroleum hydrocarbons is also disclosed. The system can be used in removal of wax deposition in refinery process equipment, process flow lines, during piping operations, up-gradation of wax, prevention of clogging of pipelines, processing of sludge or for removing sludge from petroleum tank installations and enhancing the crude oil flow.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application is a divisional application of U.S. application Ser.No. 15/037,606, entitled “SYSTEMS AND METHODS FOR SCREENING SOLVENTS FORDISSOLVING TANK BOTTOM SLUDGE”, filed on May 16, 2016, which is a 35U.S.C. § 371 national stage filing of PCT Patent Application NumberPCT/M2014/066097, filed Nov. 17, 2014, which claims priority to Indianprovisional patent applications 5300/CHE/2013 entitled “FORMULATIONS FORDISSOLUTION OF PETROLEUM SLUDGE OR WAXES AND METHOD FOR EVALUATIONTHEREOF” filed on Nov. 18, 2013 and 5805/CHE/2013 entitled “METHOD OFSCREENING SOLVENTS FOR DISSOLVING TANK BOTTOM SLUDGE” filed on Dec. 13,2013, which are incorporated herein by reference.

FIELD OF THE INVENTION

Present disclosure relates generally to a method of screening solventsfor dissolving petroleum hydrocarbons and in particular to the use ofenvironmental friendly green solvents-ionic liquids for the dissolutionof petroleum tank-bottom sludge (TBS).

DESCRIPTION OF THE RELATED ART

“Crude oil” refers to untreated or unrefined oil recovered from beneaththe surface of the earth. Contaminants such as solids, heavy hydrocarbonfractions, as well as rust and scale from the piping and tank walls,that accumulate at the bottom of the oil tanks during crude oilprocessing/storage, are generally known as tank bottoms or tank bottomsludge (TBS). The build-up of TBS accelerates corrosion within the tank,affects tank maintenance, and reduces the working capacity of the tank,and hence need to be disposed of.

Disposal or removal of sludge has been a laborious procedure experiencedby most of the oilfield operators and refineries worldwide, as these arepoorly soluble. Conventional methods for the sludge disposal includemanual cleaning of the sludge, injection of high pressure hot water oruse of rotating tools. However, the manual cleaning methods are unsafe,costly, time consuming and cumbersome, and are not always employable ina hazardous environment.

The most common cleaning processes other than manual cleaning are crudeoil washing (COW) and chemical cleaning. In some cases, the sludge ischemically treated and allowed to stand for specific period so as to getseparated by gravity in a separate vessel. Specially designed mobilefilter presses and centrifuges have been used for more cleaner and rapidseparations. Due to the viscous nature and paraffinic/naphtheniccomposition of sludge, it is difficult to pump it out of the tanks. Useof dispersants to break the sludge into coarse material, and mixing thesludge with light crude oil has been tried in the art.

One effective way to process TBS is to dissolve the sludge in chemicalsolvents such as aromatic and aliphatic hydrocarbon liquids followed bycleaning. However, because of the complex nature of the sludge, the poorsolubility and variable composition, solubilizing the sludge is achallenging task. It is therefore important to measure the solubility ofTBS in a wide range of solvents so that an ideal solvent or solventmixture could be identified. A simple method of measuring the solubilityof a substance is to incrementally add the substance in a known volumeof solvent till saturation is attained and measuring the amount ofsubstance added. However, this can be time-consuming using conventionalsystems and methods.

The invention addresses some of the drawbacks of conventional methodsand satisfies the need for a method and a system that measuressolubility of petroleum hydrocarbons in a wide range of solvents andco-solvents, with further related advantages as set forth here.

SUMMARY OF THE INVENTION

Methods and systems for screening solvents for solubilization ofpetroleum hydrocarbons are disclosed.

In one embodiment, a method of screening solvents for processingpetroleum hydrocarbons is disclosed, wherein petroleum hydrocarbons isdissolved in a selected solvent to form a first solution, to which aco-solvent, such as an ionic liquid is added to form a second solution.The absorbance of the first and second solution is measured usingspectroscopic techniques. The efficacy of the ionic liquid insolubilizing petroleum hydrocarbons is determined based on thedifference between the absorbance of the first and the second solutions.The above process is repeated using a plurality of solvents, ionicliquids or mixtures thereof.

In one aspect, the absorbance of the first and second solution ismeasured using UV-Vis spectroscopy, Fourier transform-infraredspectroscopy (FT-IR) or ¹³C-nuclear magnetic resonance (NMR).

In one aspect, the solvent is chosen from aromatic hydrocarbon solventsor aliphatic hydrocarbon solvents such as pentane, hexane, heptane,octane, decane, ethyl acetate benzene, ethyl benzene, xylene, phenol,toluene, and mixtures thereof.

In another aspect, the ionic liquid is chosen from1,3-dimethylimidazolium1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide;1-butyl-1-methyl-pyrrolidinium1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide;diethylammonium phosphate; diethylammonium sulfate; triethylammoniumphosphate; triethylammonium sulfate; tripropylammonium sulfate;tributylammonium sulfate; 1-butyl-3-methylimidazolium1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide;1-butyl-3-methylimidazolium chloride; 1-butyl-3-methylimidazoliumhexafluorophosphate; 1-ethyl-3-methylimidazolium ethylsulfate; 1-hexyl-3-methylimidazolium hexafluoro-phosphate;1-decyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide;1-octyl-3-methylimidazolium chloride; 1-hexyl-3-methylimidazoliumhydrogen sulfate; triethyl-ammoniumtetrafluoroborate; triethylammoniumacetate; or mixtures thereof.

In one other aspect, the petroleum hydrocarbon source is petroleum tankbottom sludge (TBS) or heavy crude oil. In another aspect, theefficiency of the method of solubilizing petroleum hydrocarbons is atleast about 70%.

In another embodiment, a system for screening solvents for solubilizingpetroleum hydrocarbons is disclosed. The system comprises a petroleumhydrocarbon source, one or more solvent sources, one or more ionicliquid sources, a mixing device for mixing petroleum hydrocarbons withsaid solvent or said ionic liquid, a sensor to determine spectroscopicabsorbance of the solvent mixture, and a control module coupled to thesensor. The control module is configured to determine the solubilizationof petroleum hydrocarbons in the solvent based on the absorbance.

In one other embodiment, a method of processing petroleum hydrocarbonsis disclosed. The method comprises dissolving petroleum hydrocarbons ina selected solvent to form a first solution whose absorbance is measuredusing spectroscopic techniques, subsequently adding an ionic liquid intothe first solution to form a second solution. The absorbance of thesecond solution is then measured, and solubilization of petroleumhydrocarbons in the solvent is then calculated based on the differencebetween the absorbance of the first and the second solutions. Theprocess is repeated for a plurality of solvents and ionic liquids sothat at least one solvent and one ionic liquid can be selected based onthe solubilization values. The petroleum hydrocarbon is then processedusing the selected solvent and the ionic liquid in combination.

In one aspect, the method further comprises performing hold-time studyfor the selected solvent and ionic liquid combination to determine theefficiency of the petroleum hydrocarbon solubilization, wherein thesolubilization percent of petroleum hydrocarbons is found to be between60% and 230%.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention has other advantages and features which will be morereadily apparent from the following detailed description of theinvention and the appended claims, when taken in conjunction with theaccompanying drawings, in which:

FIG. 1 illustrates one embodiment of a method of screening solvents forthe solubilization of petroleum hydrocarbons.

FIG. 2 illustrates one embodiment of a system of screening solvents forthe solubilization of petroleum hydrocarbons.

FIG. 3 illustrates another embodiment of a method of screening pluralityof solvents for the solubilization of petroleum hydrocarbons.

FIG. 4A-4H illustrates UV absorption showing the effect of 4A)[Et₂NH₂]⁺[H₂PO₄]⁻, 4B) [Et₂NH₂]⁺[HSO₄]⁻, 4C) [Et₃NH]⁺[CH₃COO]⁻, 4D)[Et₃NH]⁺[BF₄]⁻, 4E) [Et₃NH]⁺[H₂PO₄]⁻, 4F) [Et₃NH]⁺[HSO₄]⁻, 4G)[Pr₃NH]⁺[HSO₄]⁻ and 4H) [Bu₃NH]⁺[HSO₄]⁻ on HCO in heptane (HCO/ILs=1:1).

FIG. 5 shows the comparison of the efficiency of all the ILs in terms ofincrease in solubility of HCO in all of the mentioned solventscontaining a varying ratio of 1:1 (HCO/ILs) at three differentconcentrations. Base line of 0% solubility is for the standard solution.

FIG. 6 shows FT-IR spectra of crude HCO, HCO+Toluene, andHCO+Toluene+[Et₃NH]⁺[H₂PO₄]⁻.

FIGS. 7A-7C illustrates the ¹³C NMR spectra of 7A) HCO, 7B) heptanetreated HCO and 7C) HCO treated with heptane along with[Et₃NH]⁺[CH₃COO]⁻.

FIGS. 8A and 8B show UV-Vis spectra of standard solution of TBS intoluene and heptane, respectively.

FIG. 9 shows the effect of ionic liquid (BMIM Cl) on absorbance withdifferent concentrations of TBS in toluene.

FIG. 10 is a bar chart showing change in absorbance values containingTBS at three different concentrations in toluene for various ionicliquids.

FIG. 11 shows the effect of ionic liquid (BMIM Cl) on absorbance withdifferent concentrations of TBS in heptane.

FIG. 12 is a bar chart showing the absorbance values of a solutioncontaining TBS in heptane and various ionic liquids.

FIG. 13 is a comparison chart representing the efficacy of various ionicliquids under study in standard solutions containing 50 ppm of TBS intoluene and heptane.

Referring to the drawings, like numbers indicate like parts throughoutthe views.

DETAILED DESCRIPTION

While the invention has been disclosed with reference to certainembodiments, it will be understood by those skilled in the art thatvarious changes may be made and equivalents may be substituted withoutdeparting from the scope of the invention. In addition, manymodifications may be made to adapt to a particular situation or materialto the teachings of the invention without departing from its scope.

Throughout the specification and claims, the following terms take themeanings explicitly associated herein unless the context clearlydictates otherwise. The meaning of “a”, “an”, and “the” include pluralreferences. The meaning of “in” includes “in” and “on.” Referring to thedrawings, like numbers indicate like parts throughout the views.Additionally, a reference to the singular includes a reference to theplural unless otherwise stated or inconsistent with the disclosureherein.

In one embodiment, the present disclosure is directed to a method forscreening solubility of petroleum hydrocarbons. The method comprisesselecting an aromatic or aliphatic solvent and dissolving petroleumhydrocarbons in the selected solvent to form a first solution.Subsequently, an ionic liquid (IL) is added to the first solution andmixed to form a second solution. The absorbance of the first and secondsolution is measured using a spectroscopic technique such asultraviolet-visible (UV-Vis) spectrophotometry, Fouriertransform-infrared spectroscopy (FT-IR) or ¹³C-nuclear magneticresonance (NMR) spectroscopy. The measured absorbance is indicative ofthe solubility of petroleum hydrocarbons in the selected combination ofsolvent and IL.

One exemplary method of screening solvents for solubilization ofpetroleum hydrocarbons is illustrated in the flow chart shown in FIG. 1.At step 101, petroleum hydrocarbons are dissolved in a selected firstsolvent, and blended uniformly to form a first solution. At step 102,the absorbance of the first solution is measured using spectrometrictechniques. At step 103, an IL is added to the first solution andblended to form a second solution. The absorbance of the second solutionis measured using spectroscopic techniques in step 104. The measuredabsorbance value of the second solution is indicative of theconcentration of the petroleum hydrocarbons in the selected solvent-ILcombination. In step 105, the efficiency of the IL in solubilizinghydrocarbons is determined based on the difference in measuredabsorption of the first and second solutions. The solubilization ofpetroleum hydrocarbons in combinations of various solvents and ILs isthen determined in step 106 by repeating steps 101 to 105 as shown inFIG. 1.

In one embodiment, the solvent is selected from a group of solventsincluding, but not limited to, aromatic hydrocarbon solvents, aliphatichydrocarbon solvents, or mixtures thereof. In one embodiment, thearomatic hydrocarbon solvents may comprise benzene, ethyl benzene,xylene, phenol, toluene, and mixtures thereof; and the aliphatichydrocarbon solvents may comprise pentane, hexane, heptane, octane,decane, ethyl acetate or mixtures thereof.

In one embodiment, the IL is chosen from a group of co-solventsincluding, but not limited to, 1,3-dimethylimidazolium1,1,1-trifluoro-N-[(trifluoromethyl)-sulfonyl]methanesulfonamide;1-butyl-1-methylpyrrolidinium1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide;diethylammonium phosphate; diethylammonium sulfate; triethylammoniumphosphate; triethylammonium sulfate; tripropylammoniumsulfate;tributylammoniumsulfate; 1-butyl-3-methylimidazolium1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide;1-butyl-3-methyl imidazolium chloride; 1-butyl-3-methylimidazoliumhexafluorophosphate; 1-ethyl-3-methylimidazolium ethylsulfate; 1-hexyl-3-methylimidazolium hexafluorophosphate;1-decyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide;1-octyl-3-methylimidazolium chloride; 1-hexyl-3-methylimidazoliumhydrogen sulfate; triethyl-ammoniumtetrafluoroborate; triethylammoniumacetate; or mixtures thereof. However, the application of this method isnot limited to these solvents alone but can be extended in a similar wayfor other solvents and co-solvents.

In one embodiment, the present disclosure is directed to a system 200for screening solubility of petroleum hydrocarbons in a variety ofsolvents. The system 200 comprises a source of petroleum hydrocarbons201, a solvent source 202, and a source of IL 203. The system 200 alsocomprises a mixing device 204 equipped with a blending means 204A forblending of petroleum hydrocarbons, the solvent and the IL to form asolvent mixture, a sensor 205 for detecting the absorbance of thesolvent mixture in the spectral region and a control module 206 such asa computing device comprising at least one processor and one memory fordetermining the solubilization of petroleum hydrocarbons in the solventusing the absorbance values. In some aspects, the sensor could be aspectrometer, for example.

In another embodiment, the present disclosure is related to a method ofprocessing petroleum hydrocarbons as described in FIG. 3. In step 301,the solubilization data of petroleum hydrocarbons in variouscombinations of solvent and ILs is generated based on the differencebetween the absorbance values of the first and second solutions as shownin FIG. 1. The absorbance value of the mixture of petroleum hydrocarbonsin the second solution is usually higher than that of the firstsolution, thus revealing greater dissolution of petroleum hydrocarbonsin the presence of the co-solvent (IL).

A combination of solvent and IL showing highest solubilization isselected in step 302, and the petroleum hydrocarbons are processed usingthe selected combination as in step 303. The absorbance values fordifferent concentrations of petroleum hydrocarbons in selected solventsand ILs are measured. The absorbance for different concentrationsincreases due to the enhancement in the dissolution of the petroleumhydrocarbons in the solvent. In various embodiments shown in FIG. 1 toFIG. 3 the spectroscopic technique is one of ultraviolet-visible(UV-Vis) spectrophotometry, Fourier transform-infrared spectroscopy(FT-IR) or ¹³C-nuclear magnetic resonance (NMR) spectroscopy.

As shown in FIG. 1 to FIG. 3, the use of the methods and systemsdisclosed herein enable rapid screening of solvent-co-solvent mixturesfor solubilizing difficult to clean petroleum tank bottom sludge TBS.The methods and systems disclosed herein also enable rapid and efficientprocessing of petroleum tank sludge using a combination of solvent andco-solvent identified using the screening methods. The invention alsodiscloses a system for rapid screening of solvents for solubilizingdifficult to process solids.

The method and system disclosed are further elaborated with reference tothe following examples.

Example 1

Heavy crude oil (HCO) samples were collected from Oil India Limited,Assam, India. HCO was more of a solid and was more viscous as comparedto conventional crude oil. The SARA properties and other details of HCOare summarized in Table 1.

TABLE 1 SARA Analysis and API Gravity Report Composition No. ofSaturates Aromatics Resins Asphaltenes API trials (%) (%) (%) (%)gravity 1 25.3 63.4 5.1 6.2 10.6 2 25.2 67.6 3.5 3.7 10.2 3 28.6 63.53.8 4.2 10.4 Average 26.4 64.8 4.1 4.7 10.4

Eight ILs, namely, [Et₂NH₂]⁺[H₂PO₄]⁻, [Et₂NH₂]⁺[HSO₄]⁻,[Et₃NH]⁺[CH₃COO]⁻, [Et₃NH]⁺[BF₄]⁻, [Et₃NH]⁺[H₂PO₄]⁻, [Et₃NH]⁺[HSO₄]⁻,[Pr₃NH]⁺[HSO₄]⁻, and [Bu₃NH]⁺[HSO₄]⁻ were synthesized and purifiedaccording to the methods available in the literature and were confirmedusing ¹H nuclear magnetic resonance (¹H NMR) spectroscopy. Preceding totheir usage, all the ILs were dried under severe agitation at 353 Kunder vacuum (0.1 Pa) for a minimum of 48 h to remove volatile compoundsand to reduce water content to negligible values.

Standard solutions containing HCO with solvents at differentconcentrations were prepared and their absorbance was recorded usingUV-Vis spectrophotometer at fixed wavelength corresponding to theλ_(max) Table 2. The λ_(max) values were obtained by running full scanspectra of different concentrations of solution containing HCO in thespecified solvent in the wavelength range of 190-900 nm.

TABLE 2 λ_(max) of the HCO in Various Solvents Solvent CAS no. SourcePurity (%) λ_(max) (nm) Decane 124-18-5 Aldrich 95 227 Ethyl 141-78-6Rankem 99 257 acetate Heptane 142-82-5 Merck 99 226 Hexane 110-54-3Merck 99 229 Toluene 108-88-3 Merck 99 288

For studies relating to standard solution of HCO in toluene, theconcentrations of solution used were: 10 ppm-100 ppm (with an incrementof 10 ppm). For the rest of the solvents (heptane, decane, ethylacetate, and hexane) the concentrations of the solutions (with respectHCO) used were in the range of 10 ppm to 120 ppm (with an increment of10 ppm). The range with respect to toluene was kept to the minimum asmuch as possible to reduce the amount of solvent used as it is toxic,whereas the toxicity for the rest of the solvents was found to becomparatively lesser and, therefore, a wider range was considered.

Sample solution preparation for dissolution studies were carried out forvarying ratios of HCO and ILs in the weight ratios of HCO/ILs as 1:1;1:0.5, and 1:0.1. For HCO/ILs=1:1, stock solution of 1000 ppm wasprepared by dissolving 50 mg of heavy crude oil and 50 mg of IL in 50 mLof the corresponding solvent. For HCO/ILs=1:0.5 and 1:0.1, a similarprocedure as described above was followed. The concentrations considered(i.e., 30, 50, 70 ppm for the case of toluene; 10, 30, 50, and 70 ppmfor the rest) were made by dilution from the stock solution. The threedifferent weight ratios of HCO to ILs were studied for all eight ionicliquids as mentioned above.

Further, for each ratio of HCO to ILs, four different concentrations(i.e., 10, 30, 50, 70 ppm) were prepared in four different solvents(i.e., heptane, decane, ethyl acetate, and hexane) and three differentconcentrations (i.e., 30, 50, 70 ppm) were prepared in toluene. Thus, atotal of 456 sample solutions were prepared and each of them wasprepared thrice from their respective stock solution, for three trialstudies. The absorbance values for all of the sample solutions wererecorded and were compared with their respective standard solution andwere used for the calculation pertaining to the dissolution of heavycrude oil with solvent in the presence of ILs. The standard and samplesolutions were freshly prepared and their absorbance was recorded on thesame day approximately within 2 hours of solution preparation. For thehold-time study, the sample solutions were stored in a black chamber.

(a) Preparation of Sample for FT-IR and ¹³C NMR

Samples for FT-IR and ¹³C NMR analysis were prepared by decanting thedissolved portion of HCO with solvent (filtrate) from the sampleprepared for UV-Vis spectra, followed by thoroughly washing the entireportion of the remaining residue to remove the ILs used. This portion ofresidue (obtained from the solutions containing 1:1 of HCO/ILs) wasdried using a rotary evaporator, followed by oven-drying for 2 hours,both were maintained at 70° C. A small amount of the solid portionobtained was divided into two portions. One portion was used forrecording ¹³C NMR, and the rest was used for recording the FT-IR spectraafter being ground with potassium bromide (KBr). ILs used in the samplesolution was recovered by the use of water which was recycled and can bereused. The same procedure was followed for all the five solvents. Theamount of sample and KBr used was maintained uniform throughout theinvestigation.

(b) Solubility Studies of Heavy Crude Oil without ILs

The softening of the heavy crude oil by its dissolution in varioussolvents (standard solutions) was studied by measuring absorbance usingthe UV-vis spectrophotometer at the particular wavelength correspondingto the λ_(max) of HCO in the respective solvent concerned (as shown inTable 2). The graphs of absorbance of standard solutions against theconcentration (in ppm) of the heavy crude oil in solvents such astoluene, heptane, decane, ethyl acetate, and hexane, respectively weredrawn. These concentrations (in ppm) versus absorbance graphs werefitted with linear regression analysis with a regression coefficient(R2) greater than 0.99. The equations and corresponding values of R²(correlation coefficient) obtained for various standard solutions ofheavy crude oil in pure solvents (without ILs) are shown in Table. 3.

TABLE 3 Reference UV-Vis Absorbance of HCO in Various SolventsRegression Correlation Solvent Equation Coefft. Toluene y = 0.006x0.9980 Heptane y = 0.0195x 0.9982 Decane y = 0.0219x 0.9993 Ethylacetate y = 0.0123x 0.9997 Hexane y = 0.0237 0.9995

(c) Solubility Studies of Heavy Crude Oil with ILs

The solubility studies of the sample solutions with eight ILs, fivesolvents and with three different weight-ratios of HCO/ILs were done bymeasuring their absorbance at a particular wavelength corresponding tothe λ_(max) of HCO in the respective solvent concerned (as provided inTable 2). All the values corresponding to the absorbance runs wereconsistent for three trials and were fund to be within ±0.001 of thereported values. The absorbance of the sample solutions were comparedwith the respective concentration of the standard solutions and theincrease in the percentage solubility over standard solution (withabsorbance values of standard solution as the base reference) werecalculated and plotted. FIGS. 4A-4H show the efficiency of eight ILs inthe dissolution of heavy crude oil following the order,[Et₂NH₂]⁺[H₂PO₄]⁻, [Et₂NH₂]⁺[HSO₄]⁻, [Et₃NH]⁺[CH₃COO]⁻, [Et₃NH]⁺[BF₄]⁻,[Et₃NH]⁺[H₂PO₄]⁻, [Et₃NH]⁺[HSO₄]⁻, [Pr₃NH]⁺[HSO₄]⁻, and [Bu₃NH]⁺[HSO₄]⁻.

FIG. 5 shows the percentage increase in solubility (with an accuracy of±0.1%) with an increase in the concentration of HCO in solvent (in ppm)for different weight ratios of HCO/ILs, showing the effectiveness ofvarious ILs on the solubility of heavy crude oil.

With reference to the results shown in FIGS. 4 and 5, the dissolution ofheavy crude oil in toluene was observed to be more efficient in thepresence of [Et₃NH]⁺[H₂PO₄]⁻. Minimum efficiency of less than 10% wasobserved for the IL, [Et₃NH]⁺[CH₃COO]⁻. In the case of the solventheptane, the IL [Et₃NH]⁺[CH₃COO]⁻ exhibited the maximum efficiency ofabout 70% for the dissolution of heavy crude oil while with other ILsshowed an overall better performance of around 30%. For the case of thesolvent decane, [Et₃NH]⁺[CH₃COO]⁻ showed an efficiency to the maximum ofaround 45% in the dissolution of heavy crude oil and for theconcentration of 10 ppm of heavy crude oil in decane, the ILs, namely,[Et₃NH]⁺[H₂PO₄]⁻, [Et₃NH]⁺[BF₄]⁻, and [Bu₃NH]⁺[HSO₄]⁻, showed around 50%efficiency. In the case of ethyl acetate, the IL, [Et₂NH₂]⁺[H₂PO₄]⁻,provided an efficiency of up to 32% at 10 ppm concentration for a 1:1ratio of HCO/IL for the dissolution of heavy crude oil and the ILs, suchas [Et₃NH]⁺[HSO4]⁻ and [Bu₃NH]⁺[HSO₄]⁻, showed better performance nextto [Et₂NH₂]⁺[H₂PO₄]⁻.

Other ILs showed <5% efficiency for the dissolution of heavy crude oil.In the case of hexane, [Et₃NH]⁺[CH₃COO]⁻ showed an efficiency of around62% followed by [Et₃NH]⁺[BF₄] and [Pr₃NH]⁺[HSO₄] at 10 ppm concentrationfor a 1:1 ratio of HCO/IL. In addition, it was noted that the efficiencyof dissolution of heavy crude oil decreased with increasingconcentrations of heavy crude oil in hexane, for all three weight-ratiosof HCO/ILs used. The best of ILs based on their effectiveness tosolubilize heavy crude oil in the presence of various solvents (on thebasis of 30 ppm concentration, in the ratio of HCO/IL=1:1) are shown inTable 4. In some aspects, these ranking may slightly vary with changesin concentration of heavy crude oil in solvent but essentially wouldfollow similar trends.

TABLE 4 Best of ILs based on their efficiency in the enhancement ofdissolution of HCO in five solvents, with respect to 30 ppmconcentration of heavy crude oil in the respective solvent (HCO/IL =1:1) Solubility Solvents Name of IL Chemical Formula Increase (%)Toluene Triethylammonium [Et₃NH]⁺[H₂PO₄]⁻ 58.60 phosphate HeptaneTriethylammonium [Et₃NH]⁺[CH₃COO]⁻ 58.61 acetate Decane Triethylammonium[Et₃NH]⁺[CH₃COO]⁻ 44.55 acetate Ethyl Diethylammonium [Et₂NH2]⁺[H₂PO₄]⁻21.91 acetate phosphate Hexane Triethylammonium [Et₃NH]⁺[CH₃COO]⁻ 31.19acetate

In general, with respect to the different weight-ratios of HCO/ILs, only10% of IL was found to be sufficient to cause efficient dissolution ofheavy crude oil in various solvents. From FIG. 6, showing the comparisonof solvents in the presence of ILs, it was concluded that theperformance of toluene and heptane showed the highest efficiency insoftening and dissolution of heavy crude oil in the said solventswhereas poor performance was observed for ethyl acetate and hexane.

In comparing the efficiencies of similar solvents, namely, hexane andheptane, heptane was observed to perform better than hexane. In someaspects, the reason was attributed to the tendency of hexane tosequester to some extent, depending on its ability, the components ofcrude oil (aromatics/resins/asphaltenes) which were principally UVactive. The remaining free groups, i.e., saturates (UV inactive) alongwith a meager amount of the UV active components were then available totake part in further processes, which resulted in very low absorbancevalues indicating less solubility of HCO with hexane. In that case,hexane was presumed to possess greater sequestration tendency ascompared to heptane.

(d) Hold-Time Study

Hold-time study was carried out for a sample case for the dissolution ofheavy crude oil in heptane as solvent with and without ILs using theUV-Vis spectrophotometric technique. The study showed that on holding inthe solvent for up to 30 days, the increase in the dissolution of theheavy crude oil was observed to be in the range of 11-16% for thestandard solution (heavy crude oil in heptane without ILs) and 61-222%for the sample solutions (heavy crude oil in heptane with various ILs).On comparing the solution of HCO+heptane and the solution ofHCO+heptane+IL, when the latter was stored for a prolonged period, theILs acquired more chance of interaction with HCO, that paved the way forextra softening of the HCO.

(e) FT-IR Spectral Analysis

FT-IR spectral analysis was determined for the crude HCO, the treatedHCO with neat solvents alone, and with solvent+ILs. The FT-IR spectrafor the three cases using toluene are shown in FIG. 6. The results werein good agreement with the results of UV-Vis studies.

For the FT-IR analysis of heavy crude oil with solvents, the ILs usedwere the ones giving a higher percentage of dissolution of HCO with anaccuracy of ±0.1% based on UV-Vis studies. For the virgin HCO and thetreated HCO with solvent and with solvent+ILs, mineral bands(predominantly clay and sands) around 1100, 800, and 500 cm⁻¹ exhibitedstrong absorption in the infrared region. The absorption modes observedaround 1450 cm⁻¹ corresponded to the C—H bending frequency, peak at 2950cm⁻¹ corresponded to C—H stretching frequency, and the peak around 3500cm⁻¹ corresponded to OH/H₂O.

The highest absorbance was noted between 2900 and 3000 cm⁻¹ showing thepresence of methylene groups, (e.g., alkanes) of the heavy crude oil.For the treated heavy crude oil with different solvents such as toluene,heptane, decane, ethyl acetate, and hexane, a significant drop in theintensity of the peaks were observed. The decrement in the intensity ofthe peaks showed that the proportion of HCO had decreased considerablyand was evidently more convincing in the case of the HCO treated withsolvent and IL together than HCO with the neat solvent alone. In thespectrum of the HCO, intense bands were seen as a sharp doublet near1010 cm⁻¹ which were due to kaolinite (a clay mineral), and these modeswere superimposed on absorbance due to other clays. A doublet near 800cm⁻¹ corresponded to silicates.

(f) NMR Spectral Analysis

FIGS. 7A-7C present the ¹³C NMR spectra of the HCO, the treated bottomsediments of the heavy crude oil with neat solvent, and HCO in solventwith ILs, respectively. The IL [Et₃NH]⁺[CH₃COO]⁻ was considered foranalysis of HCO in heptane, based on its better performance insolubility as observed in UV-Vis and FT-IR studies as discussed earlier.It was observed that, in the case of HCO, there were several peaks inthe region between 10 and 55 ppm, which predicted the presence ofaliphatic methyl and methylene carbon atoms in HCO. These peaks gotweakened in the case of heptane treated HCO and nearly vanished in thespectrum for the IL treated HCO in heptane. Like the FT-IR results,these ¹³C NMR results were also consistent with the earlier discussedresults indicating enhanced solubility of crude oil in the solvent andionic liquid system.

In FIG. 7A, a peak around 170 ppm was observed for the crude HCO, whichwas an indication of the >C═O group present in the HCO. The peaksvisible in the region of 120-140 ppm indicated the presence of aromaticsin the HCO. It was observed from FIG. 7B that these peaks do not vanishcompletely, indicating that there was oil still present in the sample.In FIG. 7C, the peaks due to the aromatics disappeared, signifying theabsence of oil after the treatment of heavy crude oil in heptane withthe IL, [Et₃NH]⁺[CH₃COO]⁻.

In general, from the present investigation, it was observed that thepresence of ILs along with solvents enhanced the dissolution of HCOmaking them easily pumpable and transportable through pipelines. Thehold-time study also provided reliable information for the use ofappropriate ILs and solvents for efficient softening of the HCO therebypreventing sludge deposition in storage tanks, in transportationpipelines, and in the reservoirs.

10% of IL for almost complete dissolution of HCO in organic solvent wasadequate. [Et₃NH]⁺[H₂PO₄]⁻ exhibited good performance in the dissolutionof HCO in toluene, whereas in the case of heptane, decane, and hexane[Et₃NH]⁺[CH₃COO]⁻ showed better performance and in ethyl acetate[Et₂NH₂]⁺[H₂PO₄]⁻ gave better results. Comparing the efficiency ofsolvents with respect to their enhancement in dissolution of HCOfollowed the order as toluene>heptane>decane>ethyl acetate>hexane.

The results of FT-IR and ¹³C NMR also supported the results obtainedusing UV-vis studies. The hold-time study revealed that the contact ofHCO with heptane alone for a prolonged period (30 days) dissolved about16% of HCO, while in case of heptane+IL ([Et₃NH]⁺[CH₃COO]⁻) it wasincreased by about 222%. Thus the minimal usage of ILs (green solvents)is sufficient for dissolution of HCO, and its exploitation in largescale for petroleum industries would provide room for environmentallyfriendly atmosphere.

Example 2

Standard solutions were prepared from stock solution of tank bottomsludge (TBS) collected from Oil India Limited, Assam, India. Thesolvents viz., heptane and toluene were considered for the experimentsand absorbance values for all the solutions (TBS+solvents) were recordedand were compared with the absorbance of the standard solution andfurther calculations were performed as illustrated in Example 1.

(a) IR Spectra for TBS and Calibration of the Standard SolutionsContaining the TBS in Solvent:

IR spectra of the TBS sample was obtained using FT-IR spectrophotometer,which showed the C—H stretching and C—H bending frequenciescorresponding to the crude oil present in the TBS. Peak at 1457 cm⁻¹corresponding to C—H bending frequency, peak at 2920 cm⁻¹ correspondingto C—H stretching frequency and the peak at 3418 cm⁻¹ corresponding toO—H/H₂O were observed. The full scan UV-Vis spectra of the ‘TBS+toluene’and ‘TBS+heptane’ standard solutions are shown in FIGS. 8A and 8Brespectively. These results were used to compare the UV-Vis spectra ofTBS in solvent with ionic liquids and also for determining the λ_(max)as illustrated in Table 2.

The standard calibration curve was obtained for the differentconcentrations of TBS in toluene ranging from 10 ppm-100 ppm. Theabsorbance values were recorded by fixing the wavelength to thecorresponding λ_(max) of TBS in toluene (i.e. λ_(max)=288 nm) (Table 2).The data was fitted to a linear plot with a regression value R²=0.99796.The standard calibration curve was obtained for the TBS in heptane atdifferent concentrations ranging from 10 ppm-120 ppm. The absorbancevalues were recorded by fixing the wavelength to the correspondingλ_(max) of TBS in heptane. The data was fitted to a linear plot with aregression value R²=0.99554. The linear fit equations for toluene andheptane are y=0.006× and y=0.0195×, respectively.

(b) Effect of ILs on the Solutions Containing the TBS in Toluene:

Seven ILS, namely 1-butyl-3-methyl imidazolium chloride [BMIM]⁺[Cl]⁻,1-butyl-3-methyl imidazoliumhexafluorophosphate [BMIN]⁺[PF6]⁻,diethylammonium phosphate [Et₂NH₂]⁺[H₂PO₄]⁻, 1-octyl-3-methylimidazoliumchloride [OMIM]⁺[Cl]⁻, 1-hexyl-3-methylimidazolium hydrogen sulfate[HMIM]⁺[HSO4]⁻, triethylammoniumtetrafluoroborate [Et₃NH]⁺[BF₄]⁻,triethylammonium acetate [Et₃NH]⁺[CH₃COO]⁻, were chosen for this study.

The absorbance for the samples, i.e. the solution containing TBS,toluene and ionic liquids, at 3 different concentrations of TBS intoluene at 30 ppm, 50 ppm, 70 ppm in solvent+ionic liquid, wasdetermined in the same way by fixing the wavelength at the correspondingmax of the TBS in toluene (i.e. at λ_(max)=288 nm; see Table 2). Theeffect of [BMIM]⁺[Cl]⁻ addition to TBS in toluene is shown as example inFIG. 9, depicting the comparison of absorbance of the standard solution(TBS in toluene) with the effect of addition of ILs to the standardsolution. Table 5 gives the numerical data for all seven ILs, showingthe effect of IL addition through increase in the absorbance values.

The absorbance values in Table 5 correspond to the concentration of theTBS in the solvent. As a result of addition of the various ILs, theabsorbance for different concentrations of the sample increases due tothe enhancement in the dissolution of the TBS in the solvent. Theconcentration (ppm) refers strictly to the concentration of the TBS inthe solvent only and not of the IL as the latter do not give anyabsorbance in UV-spectra.

The effect of addition of ILs to the standard solution (TBS in toluene)is illustrated in FIG. 10. This bar diagram depicts the increase in theabsorbance values in comparison with the standard. From FIG. 10, it isevident that among the ILs under study [BMIN]⁺[PF₆]⁻ is more efficientto increase the concentration of the TBS in the solution, followed bythe other co-solvents. The evidence to support this trend is given inTable 6 showing the numerical data for the percentage increase in thesolubility of the TBS in toluene.

TABLE 5 Comparison of absorbance of different ILs and TBS in toluenewith the standard (TBS in toluene) Co-solvent (IL) Concentration ofAbsorbance S. No. TBS in toluene 30 ppm 50 ppm 70 ppm Without cosolventin 0.18 0.30 0.43 toluene 1 BMIM Cl 0.27 0.45 0.62 2 BMIM PF₆ 0.28 0.490.67 3 Et₂NH₂H₂PO₄ 0.26 0.44 0.60 4 OMIM Cl 0.27 0.44 0.64 5 HMIM HSO₄0.28 0.46 0.63 6 Et₃NHBF₄ 0.26 0.44 0.61 7 Et₃NHCH₃COO 0.19 0.29 0.42

TABLE 6 Increase in the solubility of TBS in toluene with the use ofvarious ionic liquids Increase in the solubility (%) of Co-solvent (IL)TBS in toluene after addition of Initial concentration various ionicliquids (TBS:ILs = 1:1) S. No of TBS in toluene 30 ppm 50 ppm 70 ppm 1BMIM Cl 52.37 48.17 46.09 2 BMIM PF₆ 57.43 60.32 56.99 3 Et₂NH₂H₂PO₄42.31 46.47 39.54 4 OMIM Cl 45.05 45.64 50.33 5 HMIM HSO₄ 53.34 50.4646.50 6 Et₃NHBF₄ 45.05 44.84 43.87 7 Et₃NHCH₃COO 4.04 −3.84 −2.67

(c) Effect of ILs on the Solutions Containing the TBS in the SolventHeptane:

The absorbance for the samples i.e., the solution containing TBS,heptane and ionic liquids, at 4 different concentrations of TBS inheptane 10 ppm, 30 ppm. 50 ppm, 70 ppm in solvent+ionic liquid wasdetermined in the same way by fixing the wavelength at the correspondingλ_(max) of the TBS in heptane (i.e.; at λ_(max)=226 nm; see Table 2).The effect of [BMIM]⁺[Cl]⁻ addition to TBS in heptane is shown asexample in FIG. 11, depicting the comparison of absorbance of thestandard solution (TBS in heptane) with the effect of addition of ILs tothe standard solution. Table 7 gives the numerical data showing theeffect of addition of IL to the standard (TBS in heptane) by means ofthe increase in the absorbance values for all 7 ILs studied.

The effect of addition of all seven ILs to the standard solution isillustrated in FIG. 12. This bar diagram clearly depicts the increase inthe absorbance of the solutions containing TBS in heptane+IL incomparison with the standard solution for four levels of TBSconcentration in the solvent. The corresponding numerical data is givenin Table 8 showing the increase in the solubility of TBS in heptane interms of percentage. The absorbance values (in Table 7) correspond tothe concentration of the TBS in the solvent. As a result of addition ofthe various ILs, the absorbance for different concentrations of thesample increases due to the enhancement in the dissolution of the TBS inthe solvent.

TABLE 7 Comparison of absorbance of solutions containing different ILsand TBS in heptane with the standard (TBS in heptane) Co-solvent (IL)Concentration of Absorbance S. No TBS in heptane 10 ppm 30 ppm 50 ppm 70ppm Without cosolvent 0.18 0.54 0.93 1.33 in heptane 1 BMIM Cl 0.28 0.851.42 2.11 2 BMIM PF₆ 0.26 0.76 1.30 1.91 3 Et₂NH₂H₂PO₄ 0.25 0.66 1.101.53 4 OMIM Cl 0.27 0.68 1.19 1.71 5 HMIM HSO₄ 0.30 0.81 1.37 1.93 6Et₃NHBF₄ 0.25 0.73 1.24 1.72 7 Et₃NHCH₃COO 0.31 0.90 1.50 2.09

TABLE 8 Increase in the solubility of TBS in heptane with the use ofvarious ILs Increase in the solubility (%) of Co-solvent (IL) TBS inheptane after addition of Initial concentration various ionic liquids(TBS:ILs = 1:1) S.No of TBS in heptane 10 ppm 30 ppm 50 ppm 70 ppm 1BMIM Cl 54.82 56.52 52.56 58.51 2 BMIM PF₆ 41.67 40.86 40.04 44.04 3Et₂NH₂H₂PO₄ 35.19 22.04 18.40 15.11 4 OMIM Cl 49.21 25.85 28.08 28.92 5HMIM HSO₄ 65.24 48.65 47.55 45.44 6 Et₃NHBF₄ 38.96 34.10 33.71 29.29 7Et₃NHCH₃COO 68.14 65.66 61.81 57.21

(d) Comparison of the Efficacy of the ILs with the Solutions Containingthe TBS in Toluene and Heptane

The effectiveness of the addition of ILs to the solutions containing theTBS in toluene in comparison with the solution of TBS in heptane isshown in FIG. 13 as an example, for 50 ppm concentration of TBS in thesolvents in terms of UV absorbance. This bar diagram clearly depicts thepercentage increase in the solubility of the TBS in the solvent with theaddition of ILs.

(e) Day-Hold Study for the TBS in Heptane (Standard Solution)

Standard solution (TBS in heptane) which was first prepared at 1000 ppm(50 mg of TBS in 50 mL of heptane) was stored and the dilutions for 12different concentrations ranging from 10 ppm-120 ppm were done andday-hold study was performed by determining the absorbance values in thesame way by fixing the wavelength at the corresponding λ_(max) of theTBS in heptane. Day-hold study data were collected for day 1, 2, 4, 10and 30 (Table 9). It is observed that the absorbance of the standardsolutions at different concentrations showed a significant increase whenthey were allowed to stand for several days.

TABLE 9 Absorbance of the standard solutions at various concentrationstaken on day 1, day 2, day 4, day 10 and day 30 Absorbance Concentrationof Std. Solution (ppm) Days 10 20 30 40 50 60 70 80 90 100 110 120 10.18 0.37 0.54 0.72 0.93 1.12 1.33 1.53 1.76 1.97 2.19 2.43 2 0.26 0.460.62 0.75 1.11 1.24 1.51 1.66 2.00 2.09 2.31 2.55 4 0.33 0.64 0.71 0.811.28 1.57 1.67 1.84 2.28 2.18 2.45 2.67 10 0.39 0.58 0.80 0.84 1.32 1.631.80 2.02 2.51 2.29 2.69 2.71 30 0.45 0.69 1.06 1.30 1.81 1.90 2.06 2.392.64 2.77 2.99 3.29

While the invention has been disclosed with reference to certainembodiments, it will be understood by those skilled in the art thatvarious changes may be made and equivalents may be substituted withoutdeparting from the scope of the invention. In addition, manymodifications may be made to adapt to a particular situation or materialthe teachings of the invention without departing from its scope.

In various other embodiments, the invention can also be used for theremoval of wax deposition in refinery process equipment, process flowlines, and upgradation of wax.

What is claimed is:
 1. A method of processing petroleum hydrocarbons,said method comprising: a) dissolving petroleum hydrocarbons in aselected solvent to form a first solution; b) measuring absorbance ofthe first solution; c) adding an ionic liquid to the first solution andblending to form a second solution; d) measuring absorbance of thesecond solution; e) determining an increase in absorbance of the secondsolution over the first solution to be at least about 70%; f) repeatingsteps a) to e) for a plurality of solvents and ionic liquids; g)selecting at least one solvent and one ionic liquid based on thedetermination in step e); and h) processing the petroleum hydrocarbonsusing the selected solvent and the ionic liquid in combination; whereinthe ionic liquid is chosen from: 1,3-dimethylimidazolium1,1,1-trifluoro-N-[(trifluoromethyl) sulfonyl] methane-sulfonamide;1-butyl-1-methylpyrrolidinium1,1,1-trifluoro-N-[(trifluoromethyl)-sulfonyl] methane-sulfonamide;diethylammonium phosphate; diethylammonium sulfate; triethylammoniumphosphate; triethylammonium sulfate; tripropylammoniumsulfate;tributylammoniumsulfate; 1-butyl-3-methylimidazolium1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl] methanesulfonamide;1-butyl-3-methyl imidazolium chloride; 1-butyl-3-methylimidazoliumhexafluorophosphate; 1-ethyl-3-methylimidazolium ethyl sulfate;1-hexyl-3-methylimidazolium hexafluorophosphate;1-decyl-3-methylimidazolium bis(trifluoromethyl sulfonyl) imide;1-octyl-3-methylimidazolium chloride; 1-hexyl-3-methylimidazoliumhydrogen sulfate; triethylammoniumtetrafluoroborate; triethylammoniumacetate; and mixtures thereof.
 2. The method according to claim 1,wherein the absorption is measured using a spectroscopic techniqueselected from UV-Vis spectroscopy, Fourier transform-infraredspectroscopy and ¹³C-nuclear magnetic resonance.
 3. The method accordingto claim 1, further comprises performing hold-time study using theselected solvent and ionic liquid in combination for the solubilizationof petroleum hydrocarbons is at least about 60% to about 230%.
 4. Themethod according to claim 1, wherein the petroleum hydrocarbon sourcesinclude tank bottom sludge (TBS) and heavy crude oil.
 5. The methodaccording to claim 1, wherein the solvent is chosen from aromatichydrocarbon solvents, aliphatic hydrocarbon solvents, or mixturesthereof.
 6. The method according to claim 5, wherein the aliphatichydrocarbon is pentane, hexane, heptane, octane, decane, ethyl acetateor mixtures thereof.
 7. The method according to claim 5, wherein thearomatic hydrocarbon solvent is benzene, ethyl benzene, xylene, phenol,toluene, and mixtures thereof.